Theory-guided design of atomic Fe–Ni dual sites in N,P-co-doped C for boosting oxygen evolution reaction

Summary The principle of how the active sites of catalysts match the reaction intermediates has long been sought after. Herein, we report a theory-guided atomic design and fabrication strategy of a C-based catalyst with diatomic Fe–Ni and N,P co-doping for the oxygen evolution reaction (OER). The configuration matching (with O∗ on the Ni site and OH∗ on the adjacent Fe site) and the local electron engineering by P doping significantly facilitate the rate-determining step of OOH∗ formation. Such diatomic Fe–Ni is demonstrated to be thermodynamically stable and is precisely constructed through the pyrolysis of Fe3+/Ni2+-adsorbed ZIF-8 under NaH2PO2 co-feeding. The synergistic effects endow the catalyst with a low overpotential and high turnover frequency, exceeding all transition-metal N-based catalysts so far as we know, which provides a deep understanding of the OER mechanism on heteroatomic metal-based catalysts. This strategy will pave the way for novel catalyst design and the replacement of noble-metal-based catalysts.